Glycidyl methacrylate was grafted onto the pore surface in superporous cellulose beads using ceric ammonium nitrate as initiator. By modifying the grafted and ungrafted matrices with diethylaminoethyl (DEAE) groups, anion exchangers were produced. Under a proper grafting reaction condition, the adsorption capacity of bovine serum albumin (BSA) to the DEAE-G-SC was over two times increased as compared to the ungrafted DEAE-SC and no nonspecific adsorption of BSA was observed. Moreover, the intraparticle diffusive mass transfer was not affected by this grafted polymer chains. However, the flow hydrodynamic experiments revealed that the grafted polymer chains led to the decrease of flowthrough pores. So the convective mass transport in the particles was significantly reduced, leading to the decrease of column efficiency with flow velocity. Despite this unfavorable effect, however, due to the high adsorption capacity of the grafted beads, the DEAE-G-SC column could still be operated at a DBC of 20–35% higher than the normal DEAE-SC column in the range of 150–600 cm/h.